Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
  • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
  • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur

Definitions

• the present invention relates in part to a method for making organobis(thioetherimide)s having the formula, where R is a C (2-20) divalent organo radical, and R1 is a C (1-14) monovalent organo radical.
• the organo bis(thio­etherimide)s of formula (1) can be hydrolyzed to the corresponding anhydrides thereafter copolymerized with aromatic diamines to make polyimides.
• the present invention is based on the discovery that N-substituted phthalimidothiolate can react with alkylene dihalides, or activated dihalo aromatic compounds to provide the organobis(thioetherimide)s of formula (1), as shown by the following equation, where R and R1 are as previously defined, and X is a halogen radical.
• One aspect of the present invention is directed to a method for making organo bis(thioetheranhydride) of the formula, which comprises
• Radicals included within R of formulas (1) and (3) are, for example, divalent alkylene radicals such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene; arylene radicals such as phenylene, xylylene, tolylene, naphthylene, biphenylene, anthralene, and divalent radicals of the formula, where X is a member selected from the class consisting of -SO2-, -S-, and - -, and p is an integer from 1 to 4.
• Radicals included within R1 are, for example, C (1-8) alkyl radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and C (6-14) aryl radicals such as phenyl, xylyl, tolyl.
• highly crystalline polyimides having chemically combined units of formula (10) below, which can be made by effecting reaction between alkylene bis(thioether-anhydride)s of the formula, and aromatic diamines of the formula, NH2R3NH2 , (7) where R2 is as previously defined, and R3 is a divalent C (6-27) aromatic hydrocarbon radical or a divalent C (6-27) aromatic hydrocarbon radical substituted with radicals inert during intercondensation.
• a significant aspect of the present invention is the generation of N-substituted phthalimidothiolate of the formula, as shown in equation (2) which can be achieved by the nucleophilic displacement of thiobisphthalimides of formula (1) with sodium sulfide in a dipolar aprotic solvent as shown by the following equation, where R1 is as previously defined, and M is an alkali metal ion, for example, sodium or potassium.
• N-substituted phthalimidothiolate of equation (8) is by effecting reaction between an N-substituted halophthalimide and sodium sulfide as shown by the following equation, where R1, and M are as previously defined.
• Aromatic diamines which are included within formula (7) are, for example, m-phenylenediamine; p-phenylenediamine; 4,4′-diaminodiphenylpropane; 4,4-diaminodiphenylmethane; benzidine; 4,4′-diaminodiphenyl sulfide; 4,4′-diaminodiphenylsulfone; 4,4′-diaminodiphenyl ether; 1,5′-diaminonaphthalene; 3,3′-dimethylbenzidine; 3,3′-dimethoxybenzidine; 2,4-bis( ⁇ -amino-t-butyl)toluene; bis(p- ⁇ -amino-t-butylphenyl)ether; bis(p- ⁇ -methyl-o-aminopentyl)benzene; 1,3′-diamino-4-isopropylbenzene; 1,2-bis(3-amin
• the temperature required for the reaction of the organic dihalide and the N-substituted phthalimido dithiolate as shown by equation (2) can vary widely depending upon the reactivity of the organic dihalide.
• alkylene dihalides are found to be the most reactive and react at ambient temperatures very rapidly.
• Aromatic dihalides require 100°C or higher.
• Bis(thiophthalimido)alkanes form readily and are found to be high melting crystalline compounds.
• the bisimides can be readily converted to the corresponding tetra acids by the action of alkali hydroxide, such as aqueous sodium hydroxide followed by acidification with a mineral acid, for example aqueous hydrochloric acid and cyclodehydrated with a dehydrating agent, such as acetic anhydride, to produce the corresponding dianhydride.
• alkali hydroxide such as aqueous sodium hydroxide followed by acidification with a mineral acid, for example aqueous hydrochloric acid and cyclodehydrated with a dehydrating agent, such as acetic anhydride
• Highly crystalline polyimides consisting essentially of chemically combined units of the formula, can be made when the alkylene bis(thioetheranhydride) of formula (6) are intercondensed with aromatic diamine of formula (7) where R2 and R3 are as previously defined.
• the crude product was recrystallized from N,N-dimethylacetamide to provide a yield of 92.5%. Based on method of preparation, the product was 1,2-bis(N-methylphthalimido-4-thio)ethane. Its identity was further confirmed by IR and 13C nmr spectroscopy.
• sodium N-methylphthalimidothiolate was prepared from 2.970 grams (0.03804 mole) of sodium sulfide, 13.405 grams (0.03804 mole) of bis(N-methylphthalimido)sulfide, and 40 ml of N-methylpyrrolidone. The solution was cooled and 10.924 grams (0.03804 mole) of 4,4′-dichlorodiphenylsulfone was added. The mixture was heated at 110°C for 6 hours under nitrogen atmosphere. The resulting solution was cooled to room temperature and poured into 300 ml of water. There was obtained a solid precipitate which was filtered, washed with methanol and dried.
• the crude product (yield 93.6%) was recrystallized from toluene, using activated carbon. There was obtained a yield of 62% of white crystal having a melting point of 187-191°C. Based on method of preparation, the product was 4,4′-bis(N-methylphthalimido-4-thio)­diphenylsulfone. The same procedure was repeated with additional organic dihalides to produce the corresponding 4,4′-bis(N-methylphthalimido-4-thio) organic compounds which were hydrolyzed to the corresponding tetra acids and thereafter cyclodehydrated to the corresponding dianhydrides.
• the Table I shows the melting points and the crude yields of the bisimides obtained following the same procedure:
• N-phenyl-4-chlorophthalimide A mixture of 3.575 grams (13.88 millimoles) of N-phenyl-4-chlorophthalimide, 1.083 grams (13.88 millimoles) of anhydrous sodium sulfide, and 12 ml of N-methyl­pyrrolidone was heated under a nitrogen atmosphere with stirring at 65-75°C for 10 hours. Based on HPLC analysis, the N-phenyl-4-chlorophthalimide was completely converted to the corresponding N-substituted phthalimidothiolate.
• polyimides were found to be extremely resistant to aggressive solvents such as chlorinated hydrocarbons and dipolar solvents. These polyimides can be used as injection moldable thermoplastics and are useful in making composites with carbon fibers or glass fibers.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Indole Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 1987
  • 1987-06-01 US US07/056,511 patent/US4808696A/en not_active Expired - Fee Related
• 1988
  • 1988-05-05 CA CA000566041A patent/CA1331618C/en not_active Expired - Fee Related
  • 1988-05-20 EP EP88108113A patent/EP0293693A3/de not_active Withdrawn
  • 1988-06-01 JP JP88132897A patent/JPH05117234A/ja active Pending
  • 1988-06-01 AU AU16943/88A patent/AU615445B2/en not_active Ceased

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